Abstract
AbstractThree new cluster‐based CuII–azide coordination polymers, [Cu8(N3)16(222‐tet)2]n (1), [Cu10(N3)20(dien)2]n (2), and [Cu12(N3)24(Me5dien)2]n (3) as well as a 1D polymer [Cu2(N3)4(dien)]n (4) were prepared by hydrothermal reactions of CuII ions with NaN3 in the presence of various polyamines. Single‐crystal X‐ray diffraction studies reveal that 1 has a 1D chain structure based on an octanuclear cluster unit {Cu8(N3)16(222‐tet)2}. Complexes 2 and 3 are 3D polymers and in both cases the azido anions display five different bridging modes (μ‐1,1, μ‐1,3, μ‐1,1,1, μ‐1,1,3,μ‐1,1,1,3). Compound 4 is a 1D chain that represents the first example of a CuII–azide compound that contains cis‐EE, double EO, and terminally bonded azido ligands. The magnetic susceptibility data, measured from 2 to 300 K, showed ferromagnetic couplings in 1, 2, and 4 and antiferromagnetic interaction in 3. The magnetic data of 1 and 4 were fitted with rough models, giving the exchange coupling constants J = 4.19 cm–1 for 1 and J = 25.31 cm–1 for 4.
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